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Chapter 5 of 20 · Chemistry

Chemical Energetics

Chemical Energetics averages 2 MCQs per MDCAT paper — Hess's law, enthalpies of formation/combustion, and bond enthalpies are most tested.

Chemical Energetics is a Chemistry chapter on the official PMDC MDCAT 2026 syllabus, contributing roughly 2 MCQs to the 45-MCQ Chemistry section. Mastering the core concepts below typically secures the full chapter weightage.

System, surroundings, and the first law

A thermodynamic system is the part of the universe under study; the rest is the surroundings. The first law: ΔU = q + w, where q is heat added to the system and w is work done on it. At constant volume, qv = ΔU; at constant pressure, qp = ΔH, where H = U + PV. Most laboratory reactions occur at constant atmospheric pressure, so chemists tabulate ΔH. Atkins Chapter 2 derives ΔH = ΔU + ΔngRT for gas-phase reactions — vital when converting between calorimetry data and tabulated values.

Enthalpy changes — formation, combustion, neutralisation

ΔHf° is the enthalpy of formation of one mole of compound from its elements in standard states (1 bar, usually 298 K). By convention, ΔHf°(element in standard state) = 0; this is why ΔHf°(O2) = 0 but ΔHf°(O3) = +142.7 kJ/mol. Combustion enthalpies are always negative (exothermic): CH4 + 2 O2 → CO2 + 2 H2O, ΔH = −890 kJ/mol. Strong-acid–strong-base neutralisation gives a near-constant −57.3 kJ/mol because the only chemistry is H⁺(aq) + OH⁻(aq) → H2O(l).

Hess's law and enthalpy cycles

Because H is a state function, the total enthalpy change of a multi-step path equals that of any other path between the same endpoints. ΔHrxn° = ΣΔHf°(products) − ΣΔHf°(reactants). For 2 H2(g) + O2(g) → 2 H2O(l), ΔH = 2(−285.8) − 0 − 0 = −571.6 kJ. The Born-Haber cycle applies the same idea to ionic-lattice formation: atomisation, ionisation, electron affinity, lattice energy. NaCl: lattice energy ≈ −787 kJ/mol — too large to measure directly, so Hess's law lets us calculate it.

Bond enthalpies and reaction energetics

Average bond enthalpy is the energy per mole to break one mole of a particular bond in the gas phase. ΔHrxn ≈ Σ(bonds broken) − Σ(bonds formed). For H2 + Cl2 → 2 HCl: bonds broken = 436 + 243 = 679 kJ; bonds formed = 2 × 432 = 864 kJ; ΔH = 679 − 864 = −185 kJ. The approximation works because C-H, O-H bond energies vary by only a few kJ across compounds — but it is approximate, not exact. Clayden uses bond-dissociation enthalpies extensively to predict reaction feasibility.

Calorimetry and a worked numerical

In bomb calorimetry (constant volume), qv = Ccal ΔT gives ΔU directly; coffee-cup calorimetry at constant pressure gives ΔH. If 0.500 g of glucose (M = 180) burned in a calorimeter (Ccal = 5.00 kJ/K) raises the temperature by 1.56 K, q = 7.80 kJ for 2.78×10⁻³ mol, so ΔUcombustion = −2806 kJ/mol — close to the literature −2803 kJ/mol. The MDCAT often gives mass and ΔT and asks you to back out ΔH per mole; convert grams to moles first.

Key Concepts

  • Enthalpy
  • Hess's law
  • Bond energy
  • Endo- vs exothermic
  • Born-Haber cycle

Worked MCQs

Q1. ΔH_f° of O₂(g) at 298 K is:

  • A. −285.8 kJ/mol
  • B. 0 kJ/mol
  • C. +142.7 kJ/mol
  • D. −393.5 kJ/mol

Explanation: By convention the standard enthalpy of formation of an element in its standard state is zero. O₂ at 1 bar, 298 K is the standard state of oxygen.

Common trap: Common trap: students confuse O₂ (zero) with O₃ (+142.7 kJ/mol).

Q2. For C(s) + O₂(g) → CO₂(g), ΔH = −393.5 kJ. The enthalpy released when 12 g of C burns is:

  • A. −39.35 kJ
  • B. −393.5 kJ
  • C. −3935 kJ
  • D. +393.5 kJ

Explanation: 12 g of C is exactly 1 mol, releasing 393.5 kJ.

Common trap: Forgetting that the molar mass of C is 12 and dividing the energy by 10.

Q3. Which is true at constant pressure?

  • A. q = ΔU
  • B. q = ΔH
  • C. w = 0
  • D. ΔU = 0

Explanation: At constant P, q_p = ΔH because ΔH = ΔU + PΔV = ΔU + w_pV.

Common trap: Confusing constant-V (q = ΔU) with constant-P conditions.

Q4. Using bond enthalpies (H-H = 436, Cl-Cl = 243, H-Cl = 432 kJ/mol), ΔH for H₂ + Cl₂ → 2 HCl is:

  • A. −185 kJ
  • B. +185 kJ
  • C. −432 kJ
  • D. +247 kJ

Explanation: Bonds broken (679) − bonds formed (864) = −185 kJ.

Common trap: Getting the sign convention backwards: bonds formed release energy, so the answer is negative.

Q5. A reaction has ΔH = −100 kJ/mol and Δn_gas = +1 at 300 K. ΔU is approximately:

  • A. −100 kJ
  • B. −97.5 kJ
  • C. −102.5 kJ
  • D. −108.3 kJ

Explanation: ΔU = ΔH − Δn_g RT = −100 − (1)(8.314×300/1000) = −102.5 kJ/mol.

Common trap: Common trap: students confuse ΔH and ΔU when Δn_g ≠ 0; gas expansion does work that must be subtracted.

Frequently Asked Questions

Why is enthalpy of neutralisation nearly constant for strong acid + strong base?

Because the net reaction is always H⁺(aq) + OH⁻(aq) → H₂O(l) with ΔH ≈ −57.3 kJ/mol; the spectator ions do not contribute.

Is ΔH always equal to heat released?

Only at constant pressure with no non-PV work. Under constant volume conditions, q equals ΔU, not ΔH.

Can a reaction be endothermic and spontaneous?

Yes — if the entropy increase is large enough, ΔG = ΔH − TΔS can still be negative. NH₄NO₃ dissolving in water is a classic example.

Why are bond enthalpies called 'average'?

The same bond (e.g. C-H) has slightly different dissociation energies in different molecules; tabulated values are averages over many compounds.

What is the significance of a Born-Haber cycle?

It uses Hess's law to calculate lattice energies of ionic solids that cannot be measured directly, by combining sublimation, ionisation, electron affinity, and bond-dissociation steps.

How Chemical Energetics Is Tested

MDCAT questions on Chemical Energetics are a mix of recall (definitions, classifications), application (predict outcomes, interpret diagrams), and basic numerical/analytical reasoning. PMDC papers from 2020–2025 emphasized the concepts above; older UHS papers (2008–2019) tested them too, with slight variations in question framing.

Practice

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See the full MDCAT 2026 syllabus or browse all Chemistry chapters.